Designation: C1817 − 16
Standard Test Method for
The Determination of the Oxygen to Metal (O/M) Ratio in
Sintered Mixed Oxide ((U, Pu)O2) Pellets by Gravimetry1
This standard is issued under the fixed designation C1817; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This practice is an alternative method to Test Method
C698 for the determination of the oxygen-to-metal atom ratio
(O/M) in sintered mixed oxide fuel (MOX) pellets. The method
presented in Test Method C698 is a one-step thermogravimet-
ric method for determining O/M ratio in sintered MOX
powders and pellets. As stated in Test Method C698, thermo-
gravimetric methods using a two-step heating cycle are also
satisfactory (1, 2).2 The method presented in this test method is
a two-step heating cycle method. This test method is applicable
to sintered MOX pellets containing up to 10 weight percent
PuO2.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
standard.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:3
C698 Test Methods for Chemical, Mass Spectrometric, and
Spectrochemical Analysis of Nuclear-Grade Mixed Ox-
ides ((U, Pu)O2)
C753 Specification for Nuclear-Grade, Sinterable Uranium
Dioxide Powder
C757 Specification for Nuclear-Grade Plutonium Dioxide
Powder, Sinterable
1
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
Test.
Current edition approved Jan. 15, 2016. Published February 2016. Originally
approved in 2015. Last previous edition approved in 2015 as C1817 – 15. DOI:
10.1520/C1817-16.
2
The boldface numbers in parentheses refer to a list of references at the end of
this standard.
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
C833 Specification for Sintered (Uranium-Plutonium) Diox-
ide Pellets
C859 Terminology Relating to Nuclear Materials
C1068 Guide for Qualification of Measurement Methods by
a Laboratory Within the Nuclear Industry
C1672 Test Method for Determination of Uranium or Pluto-
nium Isotopic Composition or Concentration by the Total
Evaporation Method Using a Thermal Ionization Mass
Spectrometer
D1193 Specification for Reagent Water
D1356 Terminology Relating to Sampling and Analysis of
Atmospheres
2.2 ISO Standards:4
ISO 21484 Nuclear Fuel Technology – Determination of the
O/M Ratio in MOX Pellets – Gravimetric Method – First
Edition
3. Terminology
3.1 For definitions of terms used in this test method but not
defined herein, refer to Terminology C859.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 average of the relative atomic mass—the weighted
average of the relative atomic mass of an element calculated as
a function of its isotopic composition.
3.2.2 mole fraction—the ratio of the number of molecules
(or moles) of a compound or element to the total number of
molecules (or moles) present (Terminology D1356).
3.2.3 MOX—nuclear fuel composed of a mixture of uranium
and plutonium oxides ((U, Pu)O2).
3.2.4 O/M—ratio of the oxygen atoms divided by the metal
atoms in the sample.
3.2.5 relative atomic mass—a dimensionless physical
quantity, the ratio of the average mass of atoms of an element
(from a single given sample or source) to 1⁄12 of the mass of an
atom of carbon-12 (known as the unified atomic mass unit).
3.2.6 scavenging—the process of pushing a gas out by
introducing a fresh flow in.
4
Available from International Organization for Standardization (ISO), 1, ch. de
la Voie-Creuse, CP 56, CH-1211 Geneva 20, Switzerland, http://www.iso.org.
 C1817 − 16
3.2.7 sintering—to increase the bonding in a mass of pow-
der or a compact by heating below the melting point of the
main constituent.
4. Summary of Test Method
4.1 The purpose of the analysis is to test the stoichiometry
of the MOX pellet by the determination of the O/M ratio. The
principle of the method is that one or a number of MOX pellets
are heated under a specific set of atmospheric conditions in
order to add or subtract oxygen molecules to the MOX pellets.
This process results in an O/M ratio of 2 in the MOX pellets
after heating. The mass of the oxygen molecules added to or
subtracted from the MOX pellets to achieve an O/M ratio of 2
is quantified by weighing the MOX pellets before and after the
heating step. Once the difference in mass is known, the number
of atoms of oxygen added to or subtracted from the MOX
pellets can be determined. The resulting data are used to
calculate the O/M ratio in the pellets prior to heating.
4.2 Three or four MOX pellets are weighed before and after
an oxidation-reduction heat treatment at specified time and
temperature intervals.
4.3 The heating and atmospheric conditions required to
achieve an O/M ratio of 2 in the MOX pellets are as follows
(3-5):
(1) Oxidation of the pellets in a current of air at 900 6
20°C to increase the O/M ratio. There is no evidence that
oxygen can be absorbed interstitially by plutonium dioxide to
produce hyperstoichiometric oxide containing plutonium ions
having a valency higher than four. On the contrary, uranium
oxide can be hyperstoichiometric.
(2) Reduction of the pellets in a stream of argon/hydrogen
gas at 900 6 20°C to reduce the O/M ratio to 2. Under these
conditions (temperature and reducing atmosphere), the O/M
ratio is adjusted to 2. The choice of these parameters is based
upon a compromise between selecting a temperature low
enough to prevent reduction of plutonium oxide to a hypostoi-
chiometric state but high enough to reduce hyperstoichiometric
uranium oxide to UO2.
NOTE 1—The O/M ratio increases during the cooling process after the
heat cycles described above unless it is done under Ar or Ar/H2
atmosphere. So, control of the cooling atmosphere is needed.
4.4 The reactions involved are:
~ U , P u ! O 26x 6x⁄2O 2 → ~ U , P u ! O 21x (1)
~ U , P u ! O 21x 1xH 2 → ~ U , P u ! O 2.0001xH 2 O (2)
4.5 The calculation of the stoichiometry is based on the
weight difference of the pellets before and after heat treatment
and the mean atomic mass of the heavy metals in the MOX
pellets (see Section 11 for details of the calculation).
5. Significance and Use
5.1 MOX is used as a nuclear-reactor fuel. This test method
is designed to determine whether the O/M ratio meets the
requirements of the fuel specification. Examples for establish-
ing a fuel specification are given in Specification C833.
5.2 This method is suitable for all sintered MOX pellets
containing up to 12 weight % PuO2 when the UO2 and PuO2
meet the requirements of Specifications C753 and C757.
2
6. Interferences
6.1 Impurities in the sample may lead to inaccuracies in the
determination of O/M ratios either due to loss of volatiles or
gain due to redox reactions. Even inert impurities present in
sufficiently high amounts compromise the accuracy of O/M
ratios because the true mass of the ((U, Pu)O2) subjected to the
oxidation-reduction process remains unknown. When purified
PuO2 and UO2 powders with maximum total impurity contents
specified in Specifications C753 and C757 are used, the change
in mass due to the non-volatile and volatile impurities is
insignificant to the method. This method assumes that the
requirements of these two standards are met and therefore does
not take into account the impact of impurities. If impurity
contents are higher than those specified in Specifications C753
and C757, an evaluation should be performed to determine
their impact on the method. This test method assumes that
pellets are sintered. It does not correct for moisture or volatile
additives as the content of these impurities is negligible after
sintering.
6.2 The crucibles if not clean can be a potential interference.
If necessary, the crucibles are cleaned and fired before use as
described in 10.1. If crucible cleanliness is tracked and if
crucibles are cleaned when necessary, the potential for the
crucibles to be a source of interference is insignificant.
6.3 If crucibles are made from materials that oxidize under
the test conditions, they may prevent proper equilibration of
the stoichiometry of the sample by consuming available
oxygen. In addition, they would change weight and would
impact the difference in mass calculation. This method assumes
that the crucible is made out of a material that is inert under the
test conditions, such as platinum alloyed with 20 % rhodium.
6.4 Weighing accuracy of the samples is critical to the
method. If the balance meets the specification in 7.1, is
calibrated in accordance with manufacturer’s guidance, and is
checked by procedure, the potential for the balance to be a
source of error is insignificant.
6.5 Loss of weight due to pellet chipping would invalidate
the analysis. Handle pellets with care.
6.6 The average of the relative atomic mass of the uranium
and plutonium in the samples impacts the accuracy of the
calculation. The average of the relative atomic mass of uranium
and plutonium are measured by Thermal Ionization Mass
Spectrometry (TIMS) in accordance with Test Method C1672
and this measured value is accounted for in the calculation.
7. Apparatus
7.1 Analytical Balance, with precision 60.1 mg.
7.2 Tube Furnace, capable of controlling temperatures 900
6 20°C and fitted with a fused quartz tube chamber which
allows for sweeping the chamber with various gasses.
7.3 O/M Apparatus—See Fig. 1. This apparatus is not
typically commercially available and users of this test method
must build a similar device.
NOTE 2—It is important that the thermocouple be located such that it
can monitor the temperature in the zone in which the sample is placed, or
can be calibrated to account for any physical offset. It is also important
 C1817 − 16
FIG. 1 O/M Apparatus
that the furnace is designed so that the temperature remains stable across
the region in which the sample is placed. For safety reasons, it is important
to ensure that the design of the furnace limits the possibility of mixing air
with the hydrogen/argon gas mixture.
7.4 Platinum sample crucibles—alloyed with 20 % rho-
dium.
7.5 Fused Quartz Boats (if needed), designed to hold
multiple platinum sample crucibles if more than one sample is
measured at the same time.
7.6 Pair of Stainless Steel Tweezers.
7.7 Pair of Tongs (if using cleaning method 2 described in
10.1).
7.8 Hot Plate (if using cleaning method 2 described in
10.1).
7.9 Beaker (if using cleaning method 2 described in 10.1).
7.10 Gas Flow Meter, Pressure Gauge, and Regulator.
8. Reagents and Materials
8.1 Purge Gases:
8.1.1 Argon—Certified 99.995 % purity (O2 <5 mg.kg-1,
H2O <5 mg.kg-1, N2 <20 mg.kg-1).
8.1.1.1 Flow rate: 16 litres/hour.
8.1.1.2 Pressure: 200 kPa.
8.1.2 Air—Filtered and dried (Suggested air treatment sys-
tem features: filter efficiency ≥98 % of 0.01 µm, dew point
≤20°C, total hydrocarbons ≤5 mg.m-3).
8.1.2.1 Flow rate: 12 litres/hour.
8.1.2.2 Pressure: 200 kPa.
8.1.3 Argon/Hydrogen Mixture—Certified 99.995 % purity
with the total amount of impurities (O2 + H2O + CnHm) <10
mg.kg-1. The gas mixture shall be (5 % <H2 <7 %).
3
8.1.3.1 Flow rate: 16 litres/hour.
8.1.3.2 Pressure: 200 kPa.
8.2 Liquid Reagents:
8.2.1 Water (if using cleaning method 2)—Unless otherwise
indicated, references to water shall be understood to mean
laboratory accepted demineralized or deionized water in con-
formance with Specification D1193, Type 1.
8.2.2 Nitric Acid (if using cleaning method 2)—(16 M
HNO3) concentrated, specific gravity 1.42.
8.2.3 Nitric Acid 7M (if using cleaning method 2)—Add 440
mL of concentrated HNO3 to 900 mL of DI water, dilute to a
final volume of 1 litre.
8.3 Reference Materials:
8.3.1 There are no certified reference materials (MOX
pellets) for the O/M ratio determination by the thermogravi-
metric treatment method (6).
9. Precautions
9.1 Because of the toxicity of plutonium, all operations
should be performed within an approved glove box fitted with
appropriate filters to contain any small particle of plutonium. A
detailed discussion of the necessary precautions is beyond the
scope of this test method. Personnel involved in these analyses
should be familiar with safe handling practices (7, 8).
9.2 The furnace, sample tube, and sample crucibles are
heated to 900 6 20°C. Extreme care must be exercised to avoid
burns or injury by quartz in a glove box and to avoid breaching
the primary confinement boundary.
9.3 Exercise appropriate caution when working with com-
pressed gases.
 C1817 − 16
9.4 Hydrogen is explosive when mixed with oxygen in the
presence of an ignition source. Using a mixture of argon and
hydrogen instead of pure hydrogen, limiting the hydrogen
content to a maximum of 7 % and ensuring that the design of
the furnace does not allow for the hydrogen/argon mixture to
react with air limits the safety risk of this method. Using a
glove box with an inert atmosphere also reduces the risk and
improves the method performance.
10. Procedure
10.1 Crucible Cleaning—The crucibles shall be clean and
weighed before use. Cleaning prior to each use is not required,
but an evaluation of the cleanliness of the crucible is required.
Cleaning is required if dust is visible. If crucible cleaning is
deemed required, the following are two examples of how the
crucibles can be cleaned.
10.1.1 Example Cleaning Method 1:
10.1.1.1 Wipe out the empty crucible with disposable paper
or cotton wipes.
10.1.1.2 Introduce the crucible (crucibles in the quartz boat
if necessary) into the furnace using a pair of tweezers and seal
the furnace door.
10.1.1.3 Place the furnace under argon/hydrogen by intro-
ducing the argon/hydrogen at a pressure of 200 kPa, and a flow
rate of 16 L/h.
10.1.1.4 Turn on the furnace.
10.1.1.5 Heat the crucibles at 900 6 20°C for 1 h.
10.1.1.6 Shut off the furnace and allow the crucible to cool
to less than 150°C in the argon-hydrogen atmosphere within
the furnace. If the glove box atmosphere is inert, the crucibles
can be removed at a higher temperature.
10.1.1.7 Remove the crucibles (crucibles in the quartz boat
if necessary) from the furnace using a pair of tweezers, shut off
the argon-hydrogen and allow the crucibles to cool to less than
35°C.
10.1.1.8 Weigh each crucible to within 60.1 mg. Record the
value as m0.
10.1.2 Example Cleaning Method 2:
10.1.2.1 Wipe out the empty crucible with disposable paper
or cotton wipes.
10.1.2.2 Place the crucibles in a beaker with enough 7M
HNO3 to completely cover the crucibles.
10.1.2.3 Place the beaker containing the crucibles onto a hot
plate and boil the acid for approximately 30 min.
10.1.2.4 Allow the acid solution to cool and remove the
crucibles using a pair of tongs.
10.1.2.5 Rinse the crucibles with deionized water in confor-
mance with Specification D1193, Type 1.
10.1.2.6 Introduce the crucibles (crucibles in the quartz boat
if necessary) into the furnace using a pair of tweezers and seal
the furnace door.
10.1.2.7 Place the furnace under argon by introducing the
argon at a pressure of 200 kPa, and a flow rate of 16 L/h.
10.1.2.8 Turn on the furnace.
10.1.2.9 Heat the crucibles at 150°C for approximately 30
min.
10.1.2.10 Shut off the furnace.
4
10.1.2.11 Remove the crucibles (crucibles in the quartz boat
if necessary) from the furnace using a pair of tweezers, shut off
the argon and allow the crucibles to cool to less than 35°C.
10.1.2.12 Weigh each crucible to within 60.1 mg. Record
the value as m0.
10.2 Weighing and Introduction of the Pellets:
10.2.1 Using a pair of tweezers, place the pellets vertically
into the empty crucible, and weigh to the nearest 0.1 mg.
Record the value as m1.
10.2.2 Using a pair of tweezers, introduce the sample
crucibles containing the pellets (crucibles in the quartz boat if
necessary) into the furnace and seal the furnace door.
10.2.3 Proceed with the oxidation.
10.3 Oxidation:
10.3.1 Place the furnace under argon by introducing the
argon gas at a pressure of 200 kPa and a flow rate of 16 L/h.
10.3.2 Turn on the furnace.
10.3.3 Heat the pellets in the argon atmosphere at 900 6
20°C for 5 min.
10.3.4 After 5 min turn off the argon gas and introduce the
air at a pressure of 200 kPa and a flow rate of 12 L/h.
10.3.5 Heat the pellets in the furnace for 1 min under air
scavenging.
10.3.6 After 1 min turn off the air and introduce argon under
the conditions given in 10.3.1.
10.3.7 Heat the pellets in the argon atmosphere for 5 min.
10.3.8 This completes the oxidation cycle, turn off the argon
and quickly initiate the reduction sequence.
10.4 Reduction:
10.4.1 Place the furnace under argon/hydrogen by introduc-
ing the argon/hydrogen at a pressure of 200 kPa and a flow rate
of 16 L/h.
10.4.2 Heat the pellets under argon/hydrogen scavenging at
900 6 20°C for 8 hours.
10.4.3 After the eight hour time period, shut down the
furnace and allow the pellet samples to cool to 50°C or less
under argon/hydrogen scavenging. This completes the reduc-
tion cycle.
10.4.4 Remove the crucibles (or crucibles in the quartz boat)
from the furnace tube using a pair of tweezers and allow them
to cool to 35°C or less. Turn off the argon-hydrogen.
10.4.5 Initiate the weighing sequence as quickly as practical
after the crucibles have cooled down.
10.5 Weighing:
10.5.1 Weigh each platinum sample crucible containing the
MOX pellets as quickly as practical to the nearest 0.1 mg.
Record the final mass of the crucible as m2.
11. Calculation
11.1 Calculation of the Average Atomic Mass:
11.1.1 Calculate the average atomic mass of the heavy metal
oxide after heat treatment, assuming that the O/M ratio equals
exactly 2, using the formula:
@ A t ~ P u ! # 3 Pu%1 @ A t ~ U ! # 3 U%1 @ A t ~ A m ! # 3 Am%
At 5 12
Pu%1U%1Am%
3 At ~ 0 ! (3)

where:
At = the average of the relative atomic mass of the
heavy metal oxide,
At(Pu) = the average of the relative atomic mass of pluto-
nium in the oxide from a TIMS analysis,
At(U) = the average of the relative atomic mass of uranium
in the oxide from a TIMS analysis,
At(Am) = the average of the relative atomic mass of ameri-
cium in the oxide (241Am),
Pu % = the mole fraction, in percentage, of plutonium in
the oxide,
U% = the mole fraction, in percentage, of uranium in the
oxide,
Am % = the mole fraction, in percentage, of americium in
the oxide, and
At(O) = the atomic mass of oxygen (15.9994).
NOTE 3—The measurement method for determining the mole fraction
of americium in the oxide is not described in this standard. It can be
measured using a suitable method, standardized or qualified internally by
the laboratory using guidance in Guide C1068.
11.2 Calculation of the O/M Ratio:
11.2.1 Calculate the O/M ratio as follows:
A t 3 ~ m 2 2 m 1!
O⁄M 5 2.000 2
A t~ O ! 3 ~ m 2 2 m 0!
where:
m0 = the mass, in grams, of the empty crucible,
m1 = the mass, in grams, of the crucible with test sample
before oxidation-reduction,
m2 = the mass, in grams, of the crucible with test sample
after oxidation-reduction heat treatment,
At(O) = the relative atomic mass of oxygen (15.9994), and
At = the average of the relative atomic mass of heavy
metal oxide calculated from Eq 3.
REFERENCES
(1) Urie, M. W., Burt, M. C., and Delvin, W. L., “A Comparison of
Thermogravimetric Methods Used to Determine Oxygen-to-Metal
Ratios in Mixed-Oxide Fuels,” Hanford Engineering Development
Laboratory Report HEDL-TME-72-56, April 1972.
(2) McNeilly, C. E., and Chikalla, T. D., “Determination of Oxygen/
Metal Ratios for Uranium, Plutonium, and (U, Pu) Mixed Oxides,”
Journal of Nuclear Materials, Vol 39, No. 1, pp. 77–83, 1971.
(3) Brett, N. H., and Russell, L. E., “The Sintering Behaviour and
Stability of (Pu,U)02 Solid Solutions,” Trans. Br. Ceram. Soc., Vol 62,
No. 2, p. 97, 1963.
(4) Russell, L. E., Brett, N. H., Harrison, J. D. L., and Foster, E., “The
Fabrication of Fuel Pellets from Mixed UO2 and PuO2 Powders,”
UKAEA Rep. AERE-R 3429, 1960.
C1817 − 16
NOTE 4—This calculation does not take into account metallic or volatile
impurities as they are considered negligible to the analysis, as discussed in
6.1.
12. Precision and Bias
12.1 Precision—The repeatability standard deviation (1σ) of
the method as determined by a single laboratory has been
determined to be between 0.001 and 0.002 O/M units.
Typically, a repeatability of 60.004 O/M units (2 times the
standard deviation) is sufficient to measure the O/M ratio and
verify that it meets the specification for MOX fuel. This
thermogravimetric method, if performed as specified, meets
this requirement. The reproducibility of this test method is not
provided at this time because very few laboratories perform
this analysis. In addition, the cost and complexity of the
logistics associated with the transfer of MOX pellets between
laboratories is considered to be prohibitive. As a result, it is not
likely that reproducibility data will be available in the future. If
any user is aware of repeatability data from other laboratories,
please contact the technical committee having jurisdiction over
this standard, and those data will be considered for future
versions of the standard.
12.2 Bias—The bias of the test method cannot be tested
(4) reliably because of the lack of suitable reference or calibration
materials. The absence of bias depends upon quantitative
conversion of the sample to the stoichiometric dioxide. The
conditions of analysis were selected on the basis of thermody-
namic data to ensure complete conversion to the stoichiometric
dioxide and therefore the bias does not have a significant
impact on the uncertainty of the method.
13. Keywords
13.1 gravimetry; MOX; oxygen to metal (O/M) ratio; plu-
tonium; thermal analysis; uranium
(5) Lyon, W. L., “The Measurement of Oxygen to Metal Ratio in Solid
Solutions of Uranium and Plutonium Dioxides,” USAEC Rep. GEAP
4271, 1963.
(6) Rubin, J., Chidester, K., and Thompson, M., “O/M Ratio Measure-
ment in Pure and Mixed Oxide Fuels – Where Are We Now?,” Los
Alamos National Laboratory, LA-UR-00-5805, 2000, http://lib-
www.lanl.gov/la-pubs/00357110.pdf.
(7) American Standards Association Inc., Sectional Committee N6 and
American Nuclear Society Standards Committee, Nuclear Safety
Guide, USAEC Report TID-7016 (Rev. 1); AERDB, Goodyear
Atomic Corp., 1961.
(8) Wick, O. J., Ed., Plutonium Handbook, Gordon and Breach Science
Publishers, Vol II, 1967.
5
 C1817 − 16
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